Mold deformation in nanoimprint lithography

F. Lazzarino, C. Gourgon, P. Schiavone, and C. Perret

Citation: Journal of Vacuum Science & Technology B 22, 3318 (2004); doi: 10.1116/1.1815299
View online: http://dx.doi.org/10.1116/1.1815299
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Published by the AVS: Science & Technology of Materials, Interfaces, and Processing
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Mold deformation in nanoimprint lithography

F. Lazzarino,a) C. Gourgon, P. Schiavone, and C. Perret
Laboratoire des Technologies de la Microlectronique, CNRS, c/o CEA, Grenoble, 17 Rue des Martyrs, 38
054 Grenoble Cedex 9, France

(Received 21 June 2004; accepted 20 September 2004; published 13 December 2004)

In nanoimprint lithography (NIL), one of the key points to be addressed is the printing uniformity
on large area. During the process, the silicon mold undergoes significant mechanical stress of
different kinds (tension, compression, flexion, and torsion). These stresses are function of the mold
design and appear under the concurrent influence of both the applied pressure on the backside of the
mold and an opposite force due to the polymer viscoelastic behavior. This translates into
non-negligible deformations within patterned or unpatterned zones. This is a major issue because it
causes nonuniformity of the printing, mold pattern break and degradation of the polymer surface.
In this article, we demonstrate that during the imprint process mold deformations really occur at
the local scale of the patterns but also at a larger scale. 2004 American Vacuum
Society. [DOI: 10.1116/1.1815299]

II. EXPERIMENT

I. INTRODUCTION
Nanoimprint lithography (NIL) is a promising technique
which allows us to obtain nanometer scale features on large
size wafers. The patterns defined in a silicon mold are replicated by imprinting a polymer film heated at high temperature (above the glass transition temperature of the film). The
printed features can be transferred into the underlying material by plasma etching. NIL could fulfill the need of several
applications in the submicro or nanometer range.1 A key issue of this lithography technique is the printing uniformity,
since the printed patterns have to be uniform on large surfaces to lead to industrial applications. This uniformity concerns the reproducibility of the pattern sizes, as for standard
optical lithography, but also the control of the printed depth
in the polymer. This last point is absolutely needed to guarantee a uniform transfer of all the patterns into the substrate.
The printing uniformity is very important at the sample/
wafer scale, but also at the local scale in different patterns. It
has been already demonstrated that the printed depth depends on the pattern density,2 but the analysis of the nonuniformity still has to be improved. Previous publications
showed that a mold deformation occurs during the printing
process2,3 and a study has been presented on the measurement of the pressure uniformity across the mold.4 It is nevertheless necessary to have a better understanding of the
mold deformation. In this article, we present the relation between the mold design, its deformation and the resulting features. We demonstrate also that a deformation occurs in large
flat areas between the patterns. The evolution of this deformation during the printing process will be shown and it will
be related to the inexpected patterns, which are observed in
the flat nonprinted polymer film. The evolution of these
new patterns attributed to capillary bridges will be
described. These results will show that the mold design is of
great importance to avoid the multiple consequences of the
deformations.
a)

Electronic mail: lazzarinofr@chartreuse.cea.fr

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J. Vac. Sci. Technol. B 22(6), Nov/Dec 2004

The molds were obtained by deep ultraviolet lithography

on a 200 mm silicon wafer. Each field contains patterns
whose size vary between 250 nm and 100 m. After the resist exposure, patterns are transferred into the silicon using
high density plasma etching. The silicon etch depth is
230 nm. After etching and resist stripping, molds are covered
with an antisticking layer formed either by plasma deposition
using a C4F8-based chemistry or by using a fluoro-silane
compound such as FOTS (perfluoro-octyltrichlorosilane).
The polymer used for this study is a high resolution negative resist for e-beam lithography (NEB22 from SUMITOMO Chemicals, Mw= 3000 g / mol). This is a chemically
amplified photoresist composed of a blend of Polyhydroxystyren (PHS) based polymers, a photoacid generator (PAG),
a crosslinker, a solvent and several other additives. This resist is interesting for NIL since it has a good etch resistance
to the silicon plasma etching processes (etching selectivity
about 2) and a relatively low glass transition temperature
Tg. The bulk thermal properties of the resist have been
studied by Modulated Temperature Differential Scanning
Calorimetry (MT-DSC) from the powder resist sample5 and
Tg was found to be close to 80 C. The photoresist films
were spin-coated on 200 mm silicon wafers. After spincoating, each film was annealed on a hot plate for 2 min at
110 C to remove a fraction of the residual solvent. The
resulting thickness is 250 nm. This thickness is larger than
the mold depth 230 nm, avoiding any potential contact between the mold and the silicon wafer. Thanks to this difference, a residual polymer thickness hr is present at the bottom
of the printed features. Then, the printed polymer can be
used as a patterned functional polymer film or as a mask for
pattern transfer into the underlying substrate. The printed
features are observed by SEM cross section to measure the
residual thickness which is the remaining polymer thickness
at the bottom of the printed patterns.
NIL is performed using a press DIGIPRESS commercialized by METKON. The maximum size of the mold and

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2004 American Vacuum Society

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Lazzarino et al.: Mold deformation in nanoimprint lithography

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FIG. 2. Residual thickness measured in the periodic grating versus the line
position (T = 160 C, P = 50 bar, and t = 5 min).

FIG. 1. (a) Printed aperiodic grating: linewidth 500 nm/ space between 0.65
and 10 m. (b) Residual thickness measured in the aperiodic grating versus
the line position (T = 120 C and P = 50 bar).

substrate is 4 cm in diameter. The temperature can be controlled up to 240 C and the pressure can vary between 15
and 300 bars. The EVG520HE press was used to print
200 mm silicon wafers. The maximum contact force is
40 kN and the temperature can be controlled up to 300 C.
This equipment allows an independent temperature control
of the top and the bottom heaters and gives a good uniformity of the contact force across a 200 mm wafer.
III. RESULTS AND OBSERVATIONS
A. Mold deformation in patterned areas

A good uniformity of the printing depth on large surfaces

is the key point of a NIL process. This means that whatever
the mold design (shape, size, and pattern density), the residual thickness measured across the wafer has to be uniform. It is of primary importance because the residual thickness uniformity allows a good critical dimension (CD)
control during the transfer of the patterns by plasma etching.
The residual thickness has been measured by SEM cross
section in both periodic and aperiodic gratings showed in
Fig. 1(a). The aperiodic grating has a constant line width
L = 0.5 m separated by spaces S which vary between
0.65 m and 10 m. In the periodic grating, spaces and
lines are equal to 0.5 m. The residual thickness of these
two gratings is measured as a function of the line position.
The first line of the grating corresponds to the origin of the x
axis.
Figure 1(b) represents the residual thickness measured in
an aperiodic grating. The lines are printed in the NEB22
resist at 120 C for three printing times (5, 29, and 60 min).
The initial film thickness is 250 nm. Depending on the print-

ing parameters (T = 120 C and P = 50 bar), a printing time

of 5 min leads to a nonuniform residual thickness across the
aperiodic grating. This nonuniformity reveals a mold deformation which is mostly located in the dense part of the grating. The corresponding mold deformation is shown in the
insert 1 of Fig. 1(b). It is not clear if the deformation propagates through the whole silicon mold thickness but as described in Ref. 3, a deformation induced by a higher stress
can propagate through the mold, since v-grooves in contact
with the backside of the mold are reproduced in the printed
polymer. It can be noticed that the same result has been
observed on 200 mm wafers in our experiments. The mold
deformation depends on the pattern density and a strong difference is observed between dense and isolated structures. In
patterned zones, the deformation appears under the influence
of both the applied pressure on the backside of the mold and
a reaction force due to the polymer viscoelastic behavior.
This reaction force is proportional to the printed surface.
Consequently, in the dense part of the grating, the opposite
force exerted by the fluid on the mold patterns is higher than
in the isolated one. This induces different penetration speeds
of the mold, and then a mold deformation. However, the
mold can relax the mechanical stress when the printing time
is increased [see Fig. 1(b)]. The relaxation is possible when
the cavities have been filled up in the dense part, this means
when the polymer has to flow along the grating, in the x
direction. Depending on the printing parameters, a complete
mold relaxation is obtained after 60 min.
Figure 2 shows the variation of the residual thickness
measured in a periodic grating. The lines are printed in the
polymer of the NEB22 resist at 160 C, 50 bar during 5 min.
The initial film thickness is 460 nm. The residual thickness is
constant in the central part of the grating but it decreases at
the edge of the grating. This boundary effect is due to the
abrupt decrease of the pattern density at the edge. This leads
to a mold deformation at the edge of the grating. The range
of this boundary effect depends on the printing parameters
and the pattern density of the area. Figure 2 shows that the
boundary effect can extend to 50 m. Consequently, the
quality of the printing zone can be altered on a large distance. The boundary effect can have other important consequences, such as a mold pattern break. Figure 3 shows bro-

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Lazzarino et al.: Mold deformation in nanoimprint lithography

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FIG. 3. Mold dot break 200 nm/ 200 nm in the edges of the patterned zone.

ken mold dots (200 nm/ 200 nm on a square surface of

1 cm2) that remain plugged in the printed polymer because
of a destructive moldsubstrate contact at the corner and on
the edges of the patterned zone. This manifestation of the
boundary effect obviously reduces the mold lifetime. In the
second part of this article, we will see that this boundary
effect can extend to unpatterned zone and induce surface
degradations.
The mold deformation has two major consequences in
patterned areas. First, as shown previously, the residual
thickness is not uniform across the printed features. This
nonuniformity can lead to a loss of CD control during the
etching step. Second, we observe some degradation of the
mold patterns. The first consequence is probably the least
serious because an optimization of the process parameters or
mold design can lead to a uniform printing of the patterned
areas. The second consequence is more penalizing but it can
be prevented by adding on the mold dummy patterns around
the printed zones. These additional patterns can then balance
the mold stress.
B. Mold deformation in unpatterned area

We define unpatterned area as a negative zone which is

delimited by patterned positive areas. Its lateral dimensions
can vary between 200 m and 2 mm. Figure 4 shows an
optical view of a printed surface. Each zone is marked by a
central stain. This stain results from the contact between the

FIG. 4. Optical view of the printed polymer with unpatterned areas.

FIG. 5. Evidence of the contact between the mold and the film surface in
unpatterned zone. (a) Transfer of the mold surface roughness in the polymer.
(b) Thin polymer film peeling-off.

mold and the polymer film. In order to check it, special

molds were used. The mold patterns were etched into an Al
layer characterized by a large surface roughness. The mold
surface irregularities are clearly transferred into the stain [see
Fig. 5(a)]. Out of the stain, the contact is not established and
the surface remains smooth. In addition, by using a standard
silicon mold with an antisticking layer of poor quality, a film
peeling off is observed in the center of the stain [see Fig.
5(b)]. This degradation reveals a significant contact force at
this point. From these three observations, we can conclude
that the mold is deformed in unpatterned areas and that this
deformation is characterized by a large surface of contact in
the center of the zone as shown in Fig. 6(a). This surface of
contact depends on the printing parameters and the dimension of the unpatterned zone.
The stain is limited by a boundary of structures named
capillary bridges [see Figs. 7(a) and 7(b)]. These capillary
bridges are formed when the mold is located at a few tens nm
to the top of the polymer surface. In this condition, a significant destabilization occurs and polymer bridges are formed
between the film surface and the mold. Each capillary bridge
is surrounded by a polymer depletion zone: the trench. These
capillary bridges result from a polymer flow and they are not
due to a capillary condensation (molecule condensation com-

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Lazzarino et al.: Mold deformation in nanoimprint lithography

FIG. 6. (a) Mold deformation in unpatterned areas. (b) Relaxation of the

mold deformation.

ing from a gas phase). By using a mold having a significant

surface roughness, the reproduction of this roughness on the
top of the capillary bridges demonstrates the contact. Consequently, a critical distance of formation can be determined
from the knowledge of the height of the very first capillary
bridges formed and the initial film thickness. For a printing
temperature of 120 C, these capillary bridges are nucleated
when the moldpolymer distance is around 80 nm. Their for-

3321

mation is assumed to have a van der Waals and/or an electrostatic origin.6,7 This point is not clear and further studies
are ongoing. Figure 7(b) shows a top view of the boundary
of capillary bridges. This top view represents a group of
capillary bridges at different growth stage [stages (1), (2),
and (3) in Fig. 7(b)] which represent their evolution during
the printing process. Indeed, at the beginning of the NIL
process, the stain appears at the center of the unpatterned
zone, where the moldpolymer gap is the smallest, due to the
mold deformation. Then, the contact occurs leading to a
mold motion and to a relaxation of its deformation as represented in Fig. 6(b). This explains the increase of the stain
size and the evolution of the boundary of capillary bridges
moving towards the printed patterns. The three different
stages observed in Fig. 7(b) result from the mold movement
occurring during the printing process. The circles on the left
are representative of the bridges nucleation and growth. In
the center, there are so many bridges that they merge to
create lines or nonuniform features. On the right, they begin
to disappear because of the increase of the moldpolymer
contact area. Due to the contact, the polymer is pressed and
the surface becomes flat again.
Capillary bridges can appear everywhere between printed
zones. So, they can seriously deteriorate the printing because
the polymer depletion around bridges can reach the substrate
and capillary bridges can act as resist patterns which can be
transferred into the underlying substrate.

FIG. 7. (a) Capillary bridges formation. (b) The stain is limited by a boundary of capillary bridges at different growth stage.
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Lazzarino et al.: Mold deformation in nanoimprint lithography

The mold architecture can be extremely complex and the

study of its mechanical behavior requires finite elements
analysis. Nevertheless, by using the deformation theory of a
thin elastic plate, we can estimate the deformation (i.e., flexion) in the center of the unpatterned zone.8 This area is delimited on each side by patterned zones and to measure the
deformation, we can use the equation relating to the thin
plate simply supported on its four sides. For a plate subjected
to a uniform pressure loading p over an area a b, the maximum deformation f in the center of the plate is given by Eq.
(1),

f=

5pa2b2
f,
384D

where a is the length of the zone, b its width, D = E . I / 1

2 is the bending stiffness of the plate (with E the Young
modulus of silicon equals 130 Gpa, I = h3 / 12 the inertia of a
section unit of the plate, and the Poissons ratio of silicon
equals 0.28). f depends on = a / b.9 The mold thickness is
h = 725 25 m. Using the press Digipress, we know that for
a pressure of 50 bar (or 15 bar) applied on the piston, the
effective pressure applied on the mold 4 cm2 is around
157 bar (or 47 bar). By using these two pressures, we found
f varying between 5 nm and 2 nm for a zone with a
= 1 mm and b = 0.7 mm. For larger zone (a = 2 mm and b
= 2 mm), f can vary between 205 nm and 61 nm. Values
obtained for the larger zone can explain the mold-resist contact observed in unpatterned zone. We observed that this contact appears for an experimental mold deformation of
50 150 nm. For the smallest zone, values obtained are not
sufficient to allow a mold-resist contact and we attributed
this difference to the prolongation of the edge deformation of
patterned zones (the boundary effect, see Fig. 2).

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IV. CONCLUSION
It has been demonstrated that a mold undergoes significant deformations in both patterned and unpatterned zones
during a NIL process. These deformations depend on the
mold design and the polymer viscoelastic behavior which
reacts to the applied pressure proportionally to the printed
surface. These deformations can have serious consequences
such as nonuniformity of the residual thickness, mold pattern
break, and nonreversible polymer surface damages. Capillary
bridges formation is observed in unpatterned zones. This is
due to mold deformation and there are formed for a weak
moldpolymer distance which depends on the polymer viscosity. These capillary bridges can act as resist patterns
which can be transferred into the underlying substrate. Mold
deformation must be carefully characterized and taken into
account to print mold with various pattern densities.
ACKNOWLEDGMENTS
The authors would like to thank the CEA-Leti for mold
fabrication. The partial support of the EC-funded project
NaPa (Contract No. NMP4-CT-2003-500120) is gratefully
acknowledged. The content is the sole responsibility of the
authors.
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J. Vac. Sci. Technol. B, Vol. 22, No. 6, Nov/Dec 2004

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